This invention relates to benzofuran and benzothiophene sulfonamides which are novel. The compounds of this invention and their agriculturally suitable salts, are useful as agricultural chemicals, e.g., plant growth regulants and herbicides. The invention also includes intermediates useful for making these compounds.
Netherlands Patent No. 121,788, published Sept. 15, 1966, discloses the preparation of compounds of the following Formula and their use as general or selective herbicides: ##STR1## wherein R.sub.1 and R.sub.2 may independently be alkyl of 1-4 carbon atoms; and
R.sub.3 and R.sub.4 may independently be hydrogen, chlorine or alkyl of 1-4 carbon atoms. PA1 R.sub.2 is hydrogen, 2-pyrimidinyl, pyridyl, amidino, acetyl or carbamoyl. PA1 R.sub.4 is hydrogen, fluorine, chlorine, bromine or methyl; PA1 R.sub.5 is hydrogen, fluorine, chlorine, bromine, methyl or methoxy; PA1 R.sub.7 is hydrogen, fluorine, chlorine, bromine, alkyl of 1-2 carbon atoms or alkoxy of 1-2 carbon atom; PA1 R.sub.8 is hydrogen, methyl, chlorine or bromine; PA1 R.sub.9 and R.sub.10 are independently hydrogen, methyl, chlorine or bromine; PA1 W and Q are independently oxygen or sulfur; PA1 n is 0, 1 or 2; PA1 X is hydrogen, chlorine, bromine, methyl, ethyl, alkoxy of 1-3 carbon atoms, trifluoromethyl, CH.sub.3 S-- or CH.sub.3 OCH.sub.2 --; and PA1 Z is methyl or methoxy; PA1 (a) when R.sub.5 is other than hydrogen, at least one of R.sub.3, R.sub.4, R.sub.6 and R.sub.7 is other than hydrogen and at least two of R.sub.3, R.sub.4, R.sub.6 and R.sub.7 must be hydrogen; PA1 (b) when R.sub.5 is hydrogen and all of R.sub.3, R.sub.4, R.sub.6 and R.sub.7 are other than hydrogen, then all of R.sub.3, R.sub.4, R.sub.6 and R.sub.7 must be either chlorine or methyl; and PA1 (c) when R.sub.3 and R.sub.7 are both hydrogen, at least one of R.sub.4, R.sub.5 or R.sub.6 must be hydrogen. PA1 X is H, CH.sub.3, OCH.sub.3 or Cl; PA1 Y is CH.sub.3, OCH.sub.3, OCH.sub.2 CH.sub.3, CH.sub.2 OCH.sub.3, CH.sub.2 CH.sub.3, NH.sub.2, NHCH.sub.3 or N(CH.sub.3).sub.2 ; and PA1 Z is CH or N. PA1 Q.sub.1 is O, S or SO.sub.2 ; PA1 L is ##STR15## R.sub.1 is H or C.sub.1 -C.sub.4 alkyl; R.sub.2 is H or C.sub.1 -C.sub.4 alkyl; PA1 R.sub.3 is H or CH.sub.3 ; PA1 R.sub.4 is H, Cl, CH.sub.3, CF.sub.3, OCH.sub.3, Br, F, SCH.sub.3 or OCF.sub.2 H; PA1 R.sub.5 is H, CH.sub.3, OCH.sub.3, Cl, Br, NO.sub.2, CO.sub.2 R.sub.7, SO.sub.2 R.sub.8, OSO.sub.2 R.sub.9, SO.sub.2 NR.sub.10 R.sub.11, F, CF.sub.3, SCH.sub.3, OCF.sub.2 H or SO.sub.2 N(OCH.sub.3)CH.sub.3 ; PA1 R.sub.6 is H, Cl, Br or C.sub.1 -C.sub.4 alkyl; PA1 R.sub.6 ' is H, CH.sub.3, Cl or Br; PA1 R.sub.7 is C.sub.1 -C.sub.3 alkyl, CH.sub.2 CH.dbd.CH.sub.2, CH.sub.2 CH.sub.2 OCH.sub.3 or CH.sub.2 CH.sub.2 Cl; PA1 R.sub.8 is C.sub.1 -C.sub.3 alkyl; PA1 R.sub.9 is C.sub.1 -C.sub.3 alkyl or CF.sub.3 ; PA1 R.sub.10 and R.sub.11 are independently C.sub.1 -C.sub.2 alkyl; PA1 R.sub.12 is H or CH.sub.3 ; PA1 W is O or S; PA1 A is ##STR16## Y is C.sub.1 -C.sub.2 alkyl, C.sub.1 -C.sub.2 alkoxy, C.sub.1 -C.sub.2 alkoxymethyl, OCF.sub.2 H, SCF.sub.2 H, OCH.sub.2 CF.sub.3, OCH.sub.2 CH.sub.2 F, CF.sub.3, OCH.sub.2 CH.dbd.CH.sub.2, OCH.sub.2 C.tbd.CH, NHCH.sub.3, N(CH.sub.3).sub.2 or CH(OCH.sub.3).sub.2 ; and PA1 Z is CH or N; PA1 (1) in Formulae II and II', when R.sub.5 is NO.sub.2, then R.sub.6 is C.sub.1 -C.sub.4 alkyl and R.sub.6 ' is CH.sub.3 ; PA1 (2) when Q is SO, then W is O; PA1 (3) when R.sub.4 is other than H, then R.sub.5 is H; PA1 (4) R.sub.1 and R.sub.2 taken together are not more than four carbon atoms; and PA1 (5) when Y is OCF.sub.2 H, then Z is CH. PA1 (1) Compounds of the generic scope of Formula I where W is O. PA1 (2) Compounds of Preferred 1 where R.sub.5 is H, F, Cl, CH.sub.3, OCH.sub.3, CO.sub.2 (C.sub.1 -C.sub.2 alkyl), or SO.sub.2 (C.sub.1 -C.sub.2 alkyl), R.sub.4 is H, Cl, CH.sub.3 or OCH.sub.3, Y is CH.sub.3, OCH.sub.3, OC.sub.2 H.sub.5, CH.sub.2 OCH.sub.3, CH(OCH.sub.3).sub.2, CF.sub.3 CH.sub.2 O or OCF.sub.2 H and R.sub.12 is H. PA1 (3) Compounds of Preferred 2 where R.sub.3 and R.sub.4 are H, R.sub.1 is H, CH.sub.3 or CH.sub.2 CH.sub.3, R.sub.2 is H or CH.sub.3, and R.sub.5 is H, F, Cl, CH.sub.3 or OCH.sub.3. PA1 (4) Compounds of Preferred 3 where Y is CH.sub.3, OCH.sub.3 or CH.sub.2 OCH.sub.3. PA1 (5) Compounds of the generic scope of Formula II where W is O. PA1 (6) Compounds of Preferred 5 where R.sub.6 is H, CH.sub.3 or CH.sub.2 CH.sub.3 and R.sub.6 ' is H. PA1 (7) Compounds of Preferred 6 where R.sub.5 is H, Cl, CH.sub.3, OCH.sub.3, CO.sub.2 (C.sub.1 -C.sub.2 alkyl) or SO.sub.2 (C.sub.1 -C.sub.2 alkyl), R.sub.4 is H, Cl, CH.sub.3 or OCH.sub.3, Y is CH.sub.3, OCH.sub.3, OC.sub.2 H.sub.5, CH.sub.2 OCH.sub.3, CH(OCH.sub.3).sub.2, CF.sub.3 CH.sub.2 O or OCF.sub.2 H and R.sub.12 is H. PA1 (8) Compounds of Preferred 7 where R.sub.4 and R.sub.6 ' are H, R.sub.5 is H, Cl, F, CH.sub.3 or OCH.sub.3 and, R.sub.6 is H or CH.sub.3. PA1 (9) Compounds of Preferred 8 where Y is CH.sub.3, OCH.sub.3 or CH.sub.2 OCH.sub.3. PA1 R.sub.2 and R.sub.3 are as previously defined; PA1 R.sub.1 ' is H or CH.sub.3 ; and PA1 R.sub.1 " is H or C.sub.1 -C.sub.3 alkyl; when R.sub.1 " is C.sub.3 H.sub.7, R.sub.1 ' is H. PA1 "The Chemistry of Heterocyclic Compounds", a series published by Interscience Publishers, Inc., New York and London; PA1 "Pyrimidines", Vol. 16 of the above series by D. J. Brown; PA1 "S-Triazines and Derivatives", Vol. 13 of the same series by E. M. Smolin and L. Rappaport; and PA1 F. C. Schaefer, U.S. Pat. No. 3,154,547; and K. R. Huffman and F. C. Schaefer, J. Org. Chem., 28, 1812 (1963).
U.S. Pat. No. 3,637,366 discloses compounds having the formula: ##STR2## wherein R.sub.1 is hydrogen or lower saturated aliphatic acyl and
The disclosed compounds are said to provide control of crabgrass, cress, endive, clover and Poa annua.
French Patent No. 1,468,747 discloses the following para-substituted phenylsulfonamides as being useful as antidiabetic agents: ##STR3## wherein R=H, halogen, CF.sub.3 or alkyl.
Logemann et al., Chem. Ab., 53, 18052g (1959), disclose a number of sulfonamides, including uracil derivatives and those having the formula: ##STR4## wherein R is butyl, phenyl or ##STR5## and R.sub.1 is hydrogen or methyl.
When tested for hypoglycemic effect in rats (oral doses of 25 mg/100 g), the compounds in which R is butyl and phenyl were most potent. The others were of low potency or inactive.
Wojciechowski, J. Acta. Polon. Pharm. 19, p. 121-5 (1962) [Chem. Ab., 59 1633 e] describes the synthesis of N-[(2,6-dimethoxypyrimidin-4-yl)aminocarbonyl]-4-methylbenzenesulfonamide: ##STR6##
U.S. Pat. No. 4,127,405 teaches compounds which are useful for controlling weeds in wheat having the formula ##STR7## wherein R is ##STR8## R.sub.1 is ##STR9## R.sub.3 and R.sub.6 are independently hydrogen, fluorine, chlorine, bromine, iodine, alkyl of 1-4 carbon atoms, alkoxy of 1-4 carbon atoms, nitro, trifluoromethyl, cyano, CH.sub.3 S(O).sub.n -- or CH.sub.3 CH.sub.2 S(O).sub.n --;
or their agriculturally suitable salts; provided that:
In addition, unexamined European Patent Application No. 35,893 teaches o-alkylsulfonylbenzenesulfonylureas which are useful as herbicides.
In U.S. Pat. No. 4,391,627, there is a disclosure of herbicidal benzo[b]thiophene- and benzofuransulfonylureas in which the sulfonylureido group is bonded to the heterocyclic ring.
South African Patent Application No. 835165 discloses herbicidal sulfonylureas of the general structure shown below: ##STR10## wherein A is an unsubstituted or substituted bridge of 3 or 4 atoms which contains 1 or 2 oxygen, sulfur or nitrogen atoms and, together with the linking carbon atom, forms a non-aromatic 5- or 6-membered heterocyclic ring system, with the proviso that two oxygen atoms are separated by at least one carbon atom and that oxygen and sulfur atoms are only linked to each other if the sulfur atom takes the form of the --SO-- or SO.sub.2 -- group.
South African Patent Application No. 837,434 discloses herbicidal sulfonamides of formula ##STR11## where Ar is ##STR12## and R.sub.2 is halogen, C.sub.1 -C.sub.3 alkyl, C.sub.1 -C.sub.3 haloalkyl, C.sub.1 -C.sub.3 alkoxy, C.sub.1 -C.sub.3 haloalkoxy, amino, C.sub.1 -C.sub.3 alkylamino, di(C.sub.1 -C.sub.3 alkyl)amino, C.sub.3 -C.sub.6 cycloalkyl or C.sub.2 -C.sub.6 alkoxyalkyl.
Unexamined European Patent Application 79,683, published May 25, 1983, discloses herbicidal sulfonamides of formula ##STR13## where J is various benzofuran, benzothiophene, 1-benzopyran, 1-benzothiopyran, 1-benzoxepin and 1-benzothiopin moieties;
The presence of undesired vegetation causes substantial damage to useful crops, especially agricultural products that satisfy man's basic food and fiber needs, such as cotton, rice, corn, wheat, and the like. The current population explosion and concomitant world food and fiber shortage demand improvements in the efficiency of producing these crops. Prevention or minimizing the loss of a portion of such valuable crops by killing, or inhibiting the growth of undesired vegetation is one way of improving this efficiency. A wide variety of materials useful for killing, or inhibiting (controlling) the growth of undesired vegetation is available; such materials are commonly referred to as herbicides. The need still exists however, for more effective herbicides.